JP2002226474A - Method for manufacturing (meth)acrylic ester derivative containing lactone ring - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrially advantageous manufacturing method capable of manufacturing a (meth)acrylic ester derivative containing a lactone ring effectively in high yield. SOLUTION: The method for manufacturing a (meth)acrylic ester derivative containing a lactone ring comprises the following processes: (A) a process in which a hydroxyadamantanone of formula (1) (wherein, the hydroxy group is linked to the bridge head site of the adamantane ring) is made to react with (meth)acrylic acid or its reactive derivative to obtain a (meth)acrylic ester derivative of formula (2) (where, R is H or methyl, and the (meth)acryloyloxy group in the formula is linked to the bridge head site of the adamantane ring), and (B) a process where the ester derivative of the formula (2) obtained in the previous process is made to react with an organic hyperacid to obtain a (meth)acrylic ester derivative having a lactone ring of formula (3) (wherein, R is H or methyl; and the (meth)acryloyloxy group in the formula is linked to the bridge head site of the adamantane ring).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a lactone ring-containing (meth) acrylic ester derivative useful as a raw material for functional polymers such as photosensitive resins and a raw material for pharmaceuticals, agricultural chemicals and other fine chemicals. It relates to a manufacturing method.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a lactone ring-containing (meth) acrylate derivative, (1) a Baeyer in which a hydroxyadamantanone is reacted with an organic peracid.
A method is known in which a lactone ring is formed by a -Villiger type reaction, the resulting lactone is isolated, and then (2) esterified using (meth) acrylic acid or the like. As a specific example, in JP-A-2000-122294, (1) 5-hydroxy-2-adamantanone is reacted with metachloroperbenzoic acid to generate a lactone, and (2) esterification with acrylic acid chloride is performed. A method for causing this is presented.

However, in this method, step (1)
Since the solubility of the lactone obtained in step (1) in water is high, the operation of separating and purifying the lactone from the reaction mixture becomes complicated. Specifically, as a pretreatment for proceeding the esterification reaction in the step (2), after removing the organic acid such as acetic acid remaining in the reaction mixture containing the lactone obtained after the reaction in the step (1), Then, an operation of neutralizing the reaction mixture with alkali water to form an organic acid salt and separating the same is performed. The organic acid salt generated at this time can be easily removed by a method such as washing with water. However, since the lactone is actually highly soluble in water, other methods, for example, lactone is dissolved in a large amount of a solvent (such as ethyl acetate).
Or an insoluble organic acid salt is separated by filtration, or after dissolving in a solvent such as ethyl acetate, a small amount of water is added to separate as an organic acid salt aqueous solution.

[0004] However, since it is difficult to completely remove the organic acid salt from the reaction mixture containing the lactone,
In the subsequent esterification reaction, particularly in the dehydration esterification reaction, sulfuric acid as a catalyst causes a neutralization reaction with the organic acid salt, and the reaction time becomes extremely long, or
There were problems such as formation of an organic acid ester.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an industrially advantageous production method capable of efficiently producing a lactone ring-containing (meth) acrylate derivative at a high yield. .

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, obtained after esterifying hydroxyadamantanones with (meth) acrylic acid or the like ( The present inventors have found that by reacting a (meth) acrylic ester derivative with an organic peracid, a corresponding lactone ring-containing (meth) acrylic ester derivative can be efficiently produced in a high yield, and the present invention has been completed.

That is, the present invention provides (A) the following formula (1)

Embedded image (The hydroxyl group described in the formula is bonded to the bridgehead position of the adamantane ring), and (meth) acrylic acid or a reactive derivative thereof is reacted with a hydroxyadamantanone represented by the following formula (2)

Embedded image (Wherein R represents a hydrogen atom or a methyl group; the (meth) acryloyloxy group described in the formula is bonded to the bridgehead of the adamantane ring) to form a (meth) acrylic acid ester derivative And (B) reacting the (meth) acrylic acid ester derivative represented by the formula (2) produced in the above step with an organic peracid to obtain the following formula (3)

Embedded image (Wherein, R represents a hydrogen atom or a methyl group; the (meth) acryloyloxy group described in the formula is bonded to the bridgehead of the adamantane ring).
Provided is a method for producing a lactone ring-containing (meth) acrylic ester derivative, which comprises a step of forming an acrylic ester derivative.

In the above method, the hydroxyadamantanone is 5-hydroxy-2-adamantanone, and in the step (A), 5- (meth) acryloyloxy-2-adamantanone is produced. According to B), 1- (meth) acryloyloxy-4
Preferred is a method of producing -oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one.

In this specification, "acryl" and "methacryl" may be collectively referred to as "(meth) acryl", and "acryloyl" and "methacryloyl" may be collectively referred to as "(meth) acryloyl".

[0010]

[Step (A)] In the production method of the present invention, in the step (A), the hydroxyadamantanone represented by the formula (1) and (meth) acrylic acid or a reactive derivative thereof are used. To produce a (meth) acrylate derivative represented by the formula (2).

The hydroxyl group described in the above formula (1) is bonded to the bridgehead of the adamantane ring. That is, the hydroxyadamantanones represented by the formula (1) are either of the following two formulas (1a) and (1b).

Embedded image

The reaction between hydroxyadamantanones and (meth) acrylic acid or a reactive derivative thereof is more specifically carried out by, for example, (1) hydroxyadamantanones
If necessary, an active reactive derivative of (meth) acrylic acid such as (meth) acrylic halide or (meth) acrylic anhydride in the presence of a base such as triethylamine or pyridine Reacting,
(2) Reaction of hydroxyadamantanones with (meth) acrylates such as methyl (meth) acrylate in the presence of a transesterification catalyst, or (3) conversion of hydroxyadamantanones in the presence of a strong acid ( By reacting with (meth) acrylic acid, a (meth) acrylate derivative can be produced. The reaction conditions in these methods are the same as in the ordinary ester production method. At the time of the reaction, a polymerization inhibitor such as hydroquinone monomethyl ether or oxygen may be introduced in order to suppress the polymerization.

Among the above methods, the methods (1) and (3) are preferable in terms of yield, operability and the like. In the method (1), the amount of the active reactive derivative of (meth) acrylic acid used is based on 1 mol of hydroxyadamantanones.
For example, it can be appropriately selected within a range of about 1 to 10 mol. Examples of the base used in this method include hydroxides, carbonates, and the like of alkali metals (for example, sodium and potassium).
Inorganic bases such as hydrogen carbonate, hydroxides of alkaline earth metals (eg, magnesium and calcium) and carbonates; organic bases such as triethylamine and pyridine; Preferably, an organic base such as triethylamine is used. The amount of the base to be used is, for example, 0 to 10 mol, and preferably about 1 to 2 mol, per 1 mol of the hydroxyadamantanones.

In the method (3), the amount of (meth) acrylic acid can be appropriately selected, for example, in the range of about 1 to 10 mol per 1 mol of hydroxyadamantanones. Examples of the strong acid used in this method include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and t-toluenesulfonic acid; Strong acid ion exchange resins and the like can be mentioned. The amount of the strong acid used is, for example, 0.1 to 15 parts by weight, preferably 1 to 12 parts by weight based on 100 parts by weight of the hydroxyadamantanones.
It is about parts by weight. In the method (3), in order to increase the reaction rate, it is preferable to advance the reaction while distilling off by-product water by azeotropic distillation or the like. As the azeotropic solvent, for example, toluene or the like can be used.

By the above reaction, the above-mentioned formula (1a) or (1
From the hydroxyadamantanones represented by b), (meth) represented by the following formula (2a) or (2b) respectively
An acrylate derivative is obtained.

Embedded image (Wherein, R represents a hydrogen atom or a methyl group)

In the present invention, among the hydroxyadamantanones, 5-hydroxy-2-adamantanone represented by the formula (1a) is preferably used. In this case, in the step (A), the corresponding (meth) acrylic acid ester derivative represented by the formula (2a)
(Meth) acryloyloxy-2-adamantanone is obtained.

The (meth) acrylate derivative produced by the reaction is, for example, filtered, concentrated, distilled, extracted,
Separation and purification can be performed by separation means such as crystallization, recrystallization, and column chromatography, or a combination thereof.

More specifically, for example, a step of subjecting the reaction product to an extraction operation using alkaline water and an organic solvent to recover the (meth) acrylate derivative from the organic solvent layer, By subjecting it to a crystallization operation using a solvent such as the above and providing a step of recovering the (meth) acrylate derivative as crystals, the (meth) acrylate derivative can be efficiently separated and purified.

Examples of the alkaline water used in the extraction operation include an aqueous solution of an alkali metal hydroxide such as an aqueous solution of sodium hydroxide, an aqueous solution of an alkali metal carbonate such as an aqueous solution of sodium carbonate, and an aqueous solution of an alkali metal bicarbonate such as an aqueous solution of sodium hydrogen carbonate. And the like. The alkali concentration in the alkaline water varies depending on the type of the alkali, but is generally about 0.5 to 40% by weight, preferably 1 to 40% by weight.
It is about 15% by weight.

Examples of the organic solvent used in the extraction operation include aromatic hydrocarbons such as toluene; alicyclic hydrocarbons such as cyclohexane; ethers such as diethyl ether and diisopropyl ether; halogenated hydrocarbons such as methylene chloride; And the like; and mixed solvents thereof. Preferred organic solvents include aromatic hydrocarbons such as toluene.

By an extraction operation using alkaline water and an organic solvent, unreacted hydroxyadamantanones and by-products can be efficiently removed.

The ether used as a crystallization solvent in the crystallization operation includes, for example, aliphatic ethers such as diethyl ether and diisopropyl ether; and cyclic ethers such as tetrahydrofuran and dioxane. Preferably, an aliphatic ether such as diisopropyl ether is used.

By this crystallization operation, a highly pure (meth) acrylate derivative can be obtained as crystals.

[Step (B)] In the step (B), the (meth) acrylic acid ester derivative produced in the step (A) is reacted with an organic peracid to obtain the compound represented by the formula (3). A lactone ring-containing (meth) acrylate derivative is produced.

The organic peracids include formic acid, peracetic acid, trifluoroperacetic acid, perpropionic acid, m-chloroperbenzoic acid, perbenzoic acid and the like. The organic peracid may be an equilibrated peracid (eg, equilibrated formic acid, equilibrated peracetic acid, etc.). That is, for example, an organic acid such as formic acid or acetic acid may be used in combination with hydrogen peroxide to generate a corresponding organic peracid in the system. When using an equilibrium peracid, a small amount of a strong acid such as sulfuric acid may be added as a catalyst.

The amount of the organic peracid used is, for example, based on 1 mol of the (meth) acrylate derivative used in the reaction.
It is about 0.8 to 2 mol, preferably about 0.9 to 1.5 mol, and more preferably about 0.95 to 1.2 mol.

As the above-mentioned hydrogen peroxide, pure hydrogen peroxide may be used. However, from the viewpoint of handleability, it is usually diluted with a suitable solvent, for example, water (for example, 30% by weight of hydrogen peroxide solution). ).

The amount of hydrogen peroxide used is, for example, about 0.9 to 5 moles, preferably about 0.9 to 3 moles, per mole of the (meth) acrylate derivative used in the reaction.
More preferably, it is about 0.95 to 2 mol.

The reaction is carried out in the presence or absence of a solvent. Examples of the solvent include alcohols such as t-butyl alcohol; chloroform, dichloromethane,
Halogenated hydrocarbons such as 1,2-dichloroethane; aromatic hydrocarbons such as benzene; aliphatic hydrocarbons such as hexane, heptane and octane; alicyclic hydrocarbons such as cyclohexane; N, N-dimethylformamide; N
Amides such as dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; linear or cyclic ethers such as ethyl ether and tetrahydrofuran; esters such as ethyl acetate; organic acids such as acetic acid; These solvents may be used alone or as a mixture of two or more.

The reaction temperature can be appropriately selected in consideration of the reaction rate and the reaction selectivity.
Preferably it is about 10 to 60 ° C. The reaction is batch type,
It may be performed by any method such as a semi-batch type and a continuous type.

According to the above reaction, the above formula (2a) or (2
From the (meth) acrylate derivative represented by b), a lactone ring-containing (meth) acrylate derivative represented by the following formula (3a), (3b) or (3c) is obtained.

Embedded image (Wherein, R represents a hydrogen atom or a methyl group)

In the present invention, among the (meth) acrylic acid ester derivatives, 5- (a) represented by the formula (2a)
(Meth) acryloyloxy-2-adamantanone is preferably used. In this case, in step (B), 1- (meth) acryloyloxy-4-oxatricyclo [4.3.] Represented by the above formula (3a) is obtained as a corresponding lactone ring-containing (meth) acrylate derivative. 1.1
^3,8 ] undecane-5-one is obtained.

The lactone ring-containing (meth) acrylate derivative produced by the reaction can be obtained by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. It can be separated and purified.

A preferred separation and purification method includes a step of subjecting the reaction product to an extraction operation using alkaline water and an organic solvent to recover a lactone ring-containing (meth) acrylate derivative from the organic solvent layer.

As the alkaline water used in the extraction operation, the alkaline waters listed as the alkaline water used in the extraction of the (meth) acrylate derivative can be used. The alkali concentration in the alkaline water varies depending on the type of alkali, but is generally about 0.5 to 40% by weight, preferably about 1 to 15% by weight.

As the organic solvent used in the extraction operation, the organic solvents listed as the organic solvent used in the extraction of the (meth) acrylate derivative can be used.
Preferred organic solvents include esters such as ethyl acetate. Further, a reaction solvent can be used as the extraction solvent.

By an extraction operation using an alkaline water and an organic solvent, unreacted substances and by-products can be efficiently removed.

The lactone ring-containing (meth) thus obtained
Acrylic ester derivatives can be used as raw materials for functional materials such as photosensitive resins and raw materials for fine chemicals such as pharmaceuticals and agricultural chemicals.

[0039]

According to the method of the present invention, the reaction time of the esterification reaction can be reduced because the reaction is not hindered by the residual organic acid salt. In addition, since the intermediate product is hardly dissolved in water and easily dissolved in an organic solvent, it is hardly lost to an aqueous layer at the time of washing with extraction water, and the purification process can be simplified. It can be manufactured efficiently with a high yield. Therefore, the method of the present invention is extremely useful as an industrial production method.

[0040]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. The purity and yield of the product were determined by gas chromatography.

Example 1 A flask equipped with a dropping funnel, a condenser and a stirrer was charged with 5-
100 g (0.60 mol) of hydroxy-2-adamantanone, 500 g of tetrahydrofuran and 79 g (0.78 mol) of triethylamine were added, and the mixture was stirred at 50 ° C.
While the internal temperature was controlled at 45 to 55 ° C., 65 g (0.72 mol) of acrylic acid chloride was added dropwise from the dropping funnel over about 1 hour. Then, at 50 ° C, 10
A time-aging reaction was performed. After the aging reaction, the reaction solution was cooled to room temperature, 50 g of water was added, and excess acrylic acid chloride was decomposed. Further, add 500 g of toluene and add 10 g
After neutralization with a weight% aqueous sodium carbonate solution, the mixture was allowed to stand and separated.
The organic layer was taken out and washed sequentially with the same amount of 10% by weight saline and ion-exchanged water as the organic layer. When the obtained organic layer was concentrated under reduced pressure by a rotary evaporator, the purity was 9%.
110 g of 5% 5-acryloyloxy-2-adamantanone was obtained. The yield was 79%.

Example 2 A flask equipped with a dropping funnel, a condenser and a stirrer was charged with 5-acryloyloxy-2- obtained by the method of Example 1.
Adamantanone 50 g (0.22 mol), ethyl acetate 1
50 g was added, the temperature was raised to 45 ° C. with stirring, and 57.4 g of peracetic acid solution (30.0% by weight of peracetic acid, 0.23 mol) from the dropping funnel while controlling the internal temperature to 45 to 55 ° C.
Was added dropwise over about 1 hour. Thereafter, an aging reaction was performed at 50 ° C. for 3 hours. After the aging reaction, the reaction solution was cooled to room temperature, neutralized with a 10% by weight aqueous solution of NaOH, and then separated by standing. The organic layer was taken out and washed twice with the same amount of ion-exchanged water as the organic layer. The obtained organic layer was concentrated under reduced pressure using a rotary evaporator to obtain 45 g of a target crude liquid of 5-acryloyloxy-2-adamantanone. This was purified on a column packed with silica gel (trade name “Wakogel C-200”, manufactured by Wako Pure Chemical Industries, Ltd.) using n-hexane: ethyl acetate = 3: 1 as an eluent. The fraction was concentrated under reduced pressure using a rotary evaporator to give a purity of 99%.
36 g of 1-acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one
Obtained. The yield was 71%.

Example 3 100 g of 5-hydroxy-2-adamantanone was placed in a flask equipped with a dropping funnel, a condenser, a decanter and a stirrer.
(0.60 mol), 104 g (1.20 mol) of methacrylic acid, 5.9 g of sulfuric acid, and 500 g of toluene, and heated at the reflux temperature of toluene for 12 hours, and reacted while distilling off by-produced water (dehydration esterification reaction). ) Was done. After completion of the reaction, the reaction solution was cooled to room temperature, neutralized with a 10% by weight aqueous solution of sodium carbonate, and then separated by standing. The organic layer was taken out and washed sequentially with the same amount of 10% by weight saline and ion-exchanged water as the organic layer. The obtained organic layer is subjected to rotary evaporator 2
After concentration under reduced pressure to 50 g, 250 g of diisopropyl ether was gradually added with stirring, and the mixture was cooled to 2 ° C. to precipitate crystals. After filtering the crystals, the crystals were rinsed with a small amount of diisopropyl ether and dried.
5-methacryloyloxy-2-adamantanone
14 g (0.44 mol) were obtained. The yield was 81%.

Example 4 5-methacryloyloxy-obtained by the method of Example 3
When 2-adamantanone was lactonized in the same manner as in Example 2, 99% pure 1-methacryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one was obtained. Was obtained 40.0 g. The yield was 72%.

Comparative Example 1 A flask equipped with a dropping funnel, a condenser and a stirrer was charged with 5-
100 g (0.60 mol) of hydroxy-2-adamantanone, 300 g of ethyl acetate, and 100 g of acetic acid were added, and the temperature was raised to 40 ° C. with stirring, and 30 weights from the dropping funnel while controlling the internal temperature to 45 to 55 ° C. % Peracetic acid solution 160
g was added dropwise over about 1 hour. Thereafter, an aging reaction was performed at 50 ° C. for 3 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, and neutralized by gradually adding a 10% by weight aqueous sodium hydroxide solution. After the crystals precipitated by the neutralization are filtered,
After drying under reduced pressure for 1 hour, 1-hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5 is obtained.
90 g of crude crystals of -one were obtained. The crystals were redissolved in 300 g of ethyl acetate, washed with 50 g of ion-exchanged water, and allowed to stand for liquid separation. The obtained organic layer was concentrated under reduced pressure using a rotary evaporator until the amount became 20 g, and then cooled to 2 ° C. to precipitate crystals. After filtering the crystals, the crystals were rinsed with a small amount of cold water and dried at 60 ° C. for 24 hours.
7% of 1-hydroxy-4-oxatricyclo [4.
3.1.1 ^3,8 ] undecane-5-one (57 g) was obtained.
The yield was 51%.

Comparative Example 2 1-Hydroxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane obtained in Comparative Example 1 was placed in a flask equipped with a dropping funnel, a condenser, a decanter and a stirrer. 5-
ON 42 g (0.23 mol), methacrylic acid 100 g
(1.16 mol), 41 g of sulfuric acid and 250 g of toluene were added, and the mixture was heated at the reflux temperature of toluene for 50 hours to conduct a reaction (dehydration esterification reaction) while distilling off by-produced water. After completion of the reaction, the reaction solution was cooled to room temperature, neutralized with a 10% by weight aqueous solution of sodium carbonate, and then separated by standing. The organic layer was taken out and washed sequentially with the same amount of 10% by weight saline and ion-exchanged water as the organic layer. The obtained organic layer was concentrated under reduced pressure to 50 g with a rotary evaporator, 50 g of diisopropyl ether was gradually added with stirring, and the mixture was cooled to 2 ° C. to precipitate crystals. After filtering the crystals, the crystals were rinsed with a small amount of cold diisopropyl ether and dried under reduced pressure at 50 ° C. for 5 hours to give 98% pure 1-methacryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8. 26 g of undecane-5-one was obtained. Yield was 45%.

Claims (2)

[Claims] (A) The following formula (1): (The hydroxyl group described in the formula is bonded to the bridgehead position of the adamantane ring) and a (meth) acrylic acid or a reactive derivative thereof is reacted with a hydroxyadamantanone represented by the following formula (2): Formula 2 (Wherein R represents a hydrogen atom or a methyl group; the (meth) acryloyloxy group described in the formula is bonded to the bridgehead of the adamantane ring) to form a (meth) acrylic acid ester derivative And (B) reacting the (meth) acrylate derivative represented by the formula (2) produced in the above step with an organic peracid to obtain the following formula (3): (Wherein, R represents a hydrogen atom or a methyl group; the (meth) acryloyloxy group described in the formula is bonded to the bridgehead of the adamantane ring).
A method for producing a lactone ring-containing (meth) acrylic ester derivative, comprising the step of forming an acrylic ester derivative. 2. The method of claim 1, wherein the hydroxyadamantanone is 5-hydroxy-2-adamantanone, the step (A) yielding 5- (meth) acryloyloxy-2-adamantanone, and the step (B) , 1-
The method for producing a lactone ring-containing (meth) acrylate derivative according to claim 1, wherein (meth) acryloyloxy-4-oxatricyclo [4.3.1.1 ^3,8 ] undecane-5-one is produced.